Crystalline aromatic polyketone and process for producing the same

Abstract

Crystalline aromatic polyketones having a linear polymer structure comprising repeating units [I] of ##STR1## and repeating units [II] of ##STR2## the repeating units [I] and [II] are bonded alternately, and the polymer has an intrinsic viscosity of at least 0.4, has excellent properties, particularly heat resistance, and can be used as shaped articles, coatings, films, fibers, etc.

What is claimed is: 
     
       1. A cyrstalline aromatic polyketone having a linear polymer structure substantially comprising repeating units [I] of the formulae: ##STR65## and repeating units [II] of the formulae: ##STR66## said repeating units [I] and [II] being bonded alternately, and said polymer having an intrinsic viscosity of 0.4 or more. 
     
     
       2. A crystalline aromatic polyketone according to claim 1, wherein the intrinsic viscosity is 0.4 to 1.8. 
     
     
       3. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is ##STR67## and the repeating unit [II] is ##STR68## 
     
     
       4. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is ##STR69## and the repeating unit [II] is ##STR70## 
     
     
       5. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is ##STR71## and the repeating unit [II] is ##STR72## 
     
     
       6. A crystalline aromatic polyketone according to claim 5, wherein the polymer has a melting point of 330° C. or higher. 
     
     
       7. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is ##STR73## and the repeating unit [II] is ##STR74## 
     
     
       8. A crystalline aromatic polyketone according to claim 7, wherein the polymer has a melting point of 280° C. or higher. 
     
     
       9. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is 1 to 99 mole % of ##STR75## and 99 to 1 mole % of ##STR76## and the repeating unit [II] is ##STR77## 
     
     
       10. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is 1 to 99 mole % of ##STR78## and 99 to 1 mole % of ##STR79## and the repeating unit [II] is ##STR80## 
     
     
       11. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is ##STR81## and the repeating unit [II] is 1 to 99 mole % of ##STR82## and 99 to 1 mole % of ##STR83## 
     
     
       12. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is ##STR84## and the repeating unit [II] is 1 to 99 mole % of ##STR85## and 99 to 1 mole % of ##STR86## 
     
     
       13. A crystalline aromatic polyketone according to claim 2, wherein the repeating unit [I] is 1 to 99 mole % of ##STR87## and 99 to 1 mole % of ##STR88## and the repeating unit [II] is 1 to 99 mole % of ##STR89## and 99 to 1 mole % of ##STR90## 
     
     
       14. A process for producing a crystalline aromatic polyketone having a linear polymer structure substantially comprising repeating units of the formulae: ##STR91## and repeating units [II] of the formulae: ##STR92## said repeating units [I] and [II] being bonded, alternately, which comprises polycondensing a 4,4'-dihaloterephthalophenone and/or a 4,4'-dihalobenzophenone with 4- hydroxythiophenol and/or p-dimercaptobenzene in the presence of an alkali using an aromatic ketone or an aromatic sulfone as a solvent. 
     
     
       15. A process according to claim 14, wherein the alkali is at least one member selected from the group consisting of carbonates and bicarbonates of alkali metals. 
     
     
       16. A process for producing a crystalline aromatic polyketone having a linear polymer structure substantially comprising repeating units [I] of the formulae: ##STR93## and repeating units [II] of the formulae: ##STR94## said repeating units [I] and [II] being bonded alternately, which comprises polycondensing a 4,4'-dihaloterephthalophenone and/or a 4,4'-dihalobenzophenone with an alkali metal salt of 4-hydroxythiophenol and/or an alkali metal salt of p-dimercaptobenzene using an aromatic ketone or an aromatic sulfone as a solvent. 
     
     
       17. A process according to claim 14, wherein the polycondensation is carried out at a temperature of 200° to 400° C. 
     
     
       18. A process according to claim 14, wherein the aromatic ketone is a benzophenone compound of the formula: ##STR95## wherein R 1  and R 2  are independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group. 
     
     
       19. A process according to claim 18, wherein the benzophenone compound is benzophenone. 
     
     
       20. A process according to claim 14, wherein the aromatic ketone is a xanthone or thioxanthone compound of the formula: ##STR96## wherein R 3  and R 4  are independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group; and Y is an oxygen atom or a sulfur atom. 
     
     
       21. A process according to claim 20, wherein the xanthone or thioxanthone copound is xanthone. 
     
     
       22. A process according to claim 20, wherein the xanthone or thioxanthone compound is thioxanthone. 
     
     
       23. A process according to claim 14, wherein the aromatic sulfone is at least one compound selected from aromatic sulfones of the formulae: ##STR97## wherein R 5  and R 6  are independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a phenyl group. 
     
     
       24. A process according to claim 23, wherein the aromatic sulfone is diphenylsulfone. 
     
     
       25. A crystalline aromatic polyketone having a linear polymer structure substantially comprising repeating units [I] of the formulae: ##STR98## and repeating units [II] of the formulae: ##STR99## said repeating units [I] and [II] being bonded alternately, and said polymer having an intrinsic viscosity of 0.4 or more, obtained by polycondensing a 4,4'-dihaloterephthalophenone and/or a 4,4'-dihalobenzophenone with 4-hydroxythiophenol and/or p-dimercaptobenzene in the presence of an alkali. 
     
     
       26. A crystalline aromatic polyketone having a linear polymer structure substantially comprising repeating units [I] of the formulae: ##STR100## and repeating units [II] of the formulae: ##STR101## said repeating units [I] and [II] being bonded alternately, and said polymer having an intrinsic viscosity of 0.4 or more, obtained by polycondensing a 4,4'-dihaloterephthalophenone and/or a 4,4'-dihalobenzophenone with an alkali metal salt of 4-hydroxyethiophenol and/or an alkali metal salt of p-dimercaptobenzene. 
     
     
       27. A crystalline aromatic polyketone according to claim 25, wherein the polycondensation is conducted by using an aromatic ketone or an aromatic sulfone as a solvent. 
     
     
       28. A crystalline aromatic polyketone according to claim 25, wherein the polymer has an intrinsic viscosity of 0.4 to 1.8. 
     
     
       29. A crystalline aromatic polyketone according to claim 27, wherein the polymer has an intrinsic viscosity of 0.4 to 1.8. 
     
     
       30. A crystalline aromatic polyketone according to claim 25, wherein the 4,4'-dihaloterephthalophenone is 4,4'-difluoroterephthalophenone, 4,4'-dichloroterephthalophenone and/or 4-fluoro-4'-chloroterephthalophenone, and the 4,4'-dihalobenzophenone is 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone and/or 4-fluoro-4'-chlorobenzophenone. 
     
     
       31. A process according to claim 14, wherein the 4,4'-dihaloterephthalophenone is 4,4'-difluoroterephthalophenone, 4,4'-dichloroterephthalophenone and/or 4-fluoro-4'-chloroterephthalophenone, and the 4,4'-dihalobenzene is 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone and/or 4-fluoro-4'-chlorobenzophenone.